Process and reagent for resolving emulsions



Patented Nov. 36, 1943 Truman B. Wayne, Houston, Tex.

No Drawing. ApplicationJuly 29, 1933, Serial No. 222,057

8 Claims.

This invention relates to the art of resolving petroleum emulsions of thecharacter commonly encountered in the production, handling and refining of petroleum.

The principal object of this invention is to provide an improved process'and reagents for treating petroleum emulsions to separate them into their component parts of oil-and water.

The present invention is based on the discovery that derivatives of a, particular type of cyclic sulfon'ic acid derived from the sulfonation of highly aromatic .crude oils or crude oil fractions; when condensed with non-hydroxy alkyl or aralkyl amines to form either the salt through ordinary neutralization reactions, or the acyl derivative through acylation of such amines, are particularly efiective demulsifiers for certain petroleuni emulsions. Ordinary petroleum sulfonic acids derived from the sludges and oil layers in petroleum refining processes contain mixtures of many substances in addition to considerable proportions of the so-called mahogany, or oilsoluble sulfonic acids, and the green, or watersoluble sulfonic acids. The various tarry and partially polymerized unsaturates present in such sulfonates are very detrimental to the preparation of the amino derivatives herein described because they form insoluble prod-' nets with the amines used in preparing my products.

I am aware that many patents and publications have described methods for the preparation,

their manufacture to obtain products more suitable for their several uses. Considerable purification is obtained by further processing to eliminate undesirable impurities where these mineral oil, sulfonates are used as detergents and wetting agents for textile materials, but ordinarily such care is nottaken, nor has it been considered necessary, in adapting mineral oil sulfonates to petroleum dehydration.

Various patents have been issued covering petroleum sulfonic acids and their various metallic commonly salts as petroleum demulsifiers, of which United States Letters Patent-No. 1,299,385 to Rogers is generally considered as the pioneer patent. The

Reddish Patent No. 1,780,144 describes reaction products of mineral oil sulfonic acids and hydroxy-amines. This patent disclosed the use of mono, di, or tri alkyl and/or aryl hydroxy amines as neutralizing agents for mineral oil sulfonic acids of either the mahogany or green" acid types, or mixtures of the two types. It is stated that Reddish's product is highly soluble in oil, water, alcohol, ketones, as well as in others. (Lines 50-51, page 2.)

The hydroxy-amines are soluble in water but totally insoluble in oil. Hence it is readily apparent that it is only the hydroxy-amine salts of the oil-soluble mahogany sulfonates which could possibly possess any oil solubility, and they would have this property only through retaining much of the oil soluble characteristics of the mahogany sulfonate. Since the function oi the hydroxy-amines is that of promoting water solubility because of their own water soluble, oil insoluble, character, it is evident that they could not increase the oil solubility of the oil insoluble, fully water soluble green acid sulfonates. If a mixture of these two types of petroleum sulfonic acids is neutralized with mono, di, or tri ethanolamine, one would expect the oil solubility of the mixture to decrease while the water solubility increases. Any oil solubility possessed by any fraction of the mixture would result from the influence of the original oil soluble mahogany acid sulfonate content.

The preceding discussion, therefore, makes it A clear thata result not contemplated in the prior The most effective reagents are usually prepared from highly waters soluble green acids condensed with oil solubl amines having five or more carbon atoms in each alkyl group. In this manner the great ailinity for water exhibited by sulfonic acids characterized by a high organic sulfur content is modified by the highly oil soluble characteristics or the amine, and results in a green acid fraction are enfirely suitable.

product a proper balance of hydrophilic and hydrophobic qualities. and only a limited solubility in water.

The water soluble petroleum sulfonic acid used in pm my reagent may be prepared from the lower sludge layer, or B layer as it is commonly termed. This sludge may be obtained from iubricatmg oil stock or is preferably prepared from selected aromatic crudes. If derived from lubricaiing oil manufacture, it is preferably pre according to the process described by Humphreys and Rogers in their U. S. Patent No. 1,474,933, dated November 2d, 1923. The sodiim sulfates obtained from the final aicohol extraction may be aci with sulfuric acid to remove the sodium, and the free acid recov Or the oil free sodium solfonate solution prepared by repeated exmaction of the aquenus solution with naphtha for the removal ofoii,

may be acidified to free the suifonic acids. This solufion of free sulfonic acids may then he directly used in my suhswuent procedure. Other pix-compares wherein tarry and/or oil solunle constituents are l removed from the A suitable procedure is outlined in mmple I.

Among suitable es are the primary, secpropyl, hutyl. amyl, hexvl and cctyl amines. Gycicaikyl amines such as cyclonewe are particularly well suited. Higher amines such as cetyine are also contempiawd. the the more oil solulnilidg it confers on the e salt or acyl derivafive. Aralkyl amines such as henay I. and its higher homologues, are useful, particularly those having aml sidechains with three to eight carbon atoms.

In order to illustrate specificafly the new type of confion product contemplated for use in accordance with the present invention, I have set forth below several examples of the type of product suitable for use. However, it is to he understood that I do not coe myseii tothe specific chemicals, or proportions thereof, set forth in these expl as it will be readily apparent that equivalents of these specific chemicats and their various derivatives, or other proportions may be employed without departing from the spirit of the invention or the scope of the pp nded The higher the molecular weig t oi It will also he imderstocd that the reagents may be employed for analogous to those herein described. it will, of course. be understood that the reagents may be employed ior preventmg the formation of petroleum emulsions in a manner imderstood by'those in this art.

Eazample I turcisgraduallyraisedto'l0 C.wheresu1fonation proceeds with the evolution of some sulfur dioxide.

Theacidmassisnextaddedto'loflflpartsof coldwater,coolingiftopreventdecomposition, until the addition is complete. The mass is then heated to the boiling point and allowed to settle. The oil layer i removed, and the combined water and sludge layers are extracted twice with light petroleum distillate to remove oil and mahogany sulfonates. The mass is then allowed to subside and stratify. The acid layer is drawn of! and the green acid sludge layer is analyzed for organically combined sulfur, free sulfuric acid acidity'and water. An amount of eyclohexylamine equivalent to the sulfonic acid acidity is added and the mass is heated nearly to the boiling point; The oil soluble amino compound rises to the top and nearly all of the free acid and water will appear in a lower layer which is drawn oil, and the oil soluble cyclohexylamine salt is recovered.

Example II 300 parts of sulfur dioxide extract, derived from the refining of kerosene distillates, are added to the recovered product from Example I, and the mass is heated at temperatures ranging from -200 C. to form the corresponding cyclohexyl amide by dehydration of the amin salt. The solvent is either distilled out or allowed t remain as a diluent.

Example III The same as Example I or II except that moncamylamine is used instead of cyclohexylamine.

Example IV The water soluble sulfonic acid, prepared as in Example I. is neutralized with di-octylamine.

Example V The corresponding di-octyl sulfonamide is prepared i'rom the amine salt prepared according to Example IV, using the procedure outlined in Example H involving dehydration of the corresponding amine salt.

Example VI Same as Example I or II except that benzyl amyl amine is used. instead of cyclohexylamine.

The term N-alkylated sulfonamide contemplates broadly the N-alkylated monosulfonamides and disulfonamides, inclusively. As is well known to those skilled in organic chemistry, N-alkylated monosulfonamides may be prepared from either primary or secondary alkylamin'es by substituting one hydrogen atom by a sulfonic acid radical or its equivalent. N-alkvlated disulfonamides may be prepared only from primary alkylamines since the reaction involves substitution or two hydrogen atoms of the primary amine by two sulfonic acid radicals or their equivalents.

Thus, if in Example I, II or III, only one-half of the quantity of primary amine required to neutralize the sulfonic acid acidity were added and the dehydration reaction is carried out in the presence of sulfuric acid and a high-boiling solvent at an elevated temperature, the reaction product may contain a mixture or monoand disulfonamides which are readily separated from the free sulfuric acid and sulfonie acids present in the reaction mass. However, if a (ii :filkflulid secondary amine, such as dioctylamine disclosed in Examples 1V and V were used, only the monosulfonamide could. result from the initially formed alkylamine salt.

An equivalent of the sulfonic acids used in the preceding examples is their corresponding sulfonyl chlorides which react to form N-alkylated sulfonamides directly.

prieee ee'o The term water-wettable as used" in the epeciflcefion and claims refers to the outerlstie of theprodu'ct which "enables it who readily wetted by water and which is usu ecoom named by some degree of hydration of the prod-w not in contact with the aqueous phase oi the e emulsion, en the product segregates so the inter! of the emulslonend is edso'rbefi at the interfaoiei where the hydrophobe body responsible for the emulsion exists, the water wettable mop'erw of this product counteracts the efiect oir the hyiflrophobe present in the emulsion and oihus'efieote to resolution.

m ii )1 3e is used to include the propem of co oide! on in the 011 Phase.

1% will e: be one 001 that in the preparation of the eater eomb' le petroleum sulfome pert of eree tiog egeno toy from 3&99 to 20,0653

pane (or, in some cases, as high es 30,600 pert-s) cg petrofieumemulsion, either by adding the con oentreeedi omiduot directly in the emulsion or after one with wotee or oil in ehe convenfim The treeflng agents mey'he used.

in o: the mummies ways eoomy employefi in me Emeot of oleum emulsions I I. A pewol duleifyimg eompooifioo which J e the K-letefi} em lem sulfonio we,

percentage of a petroleum demulslf I r fonemlde ofe water-soluble, oil-insoluble patro I leum sulfonic acid.

2.; A petroleum demule leted sulleilm sulfomcecid. W

-3 The process of m ng petrole emuloions comp, incorporating therein e e111 percentage of a. mtroleum dem ymg composition having as acomponent the N-elkyleted smiode or? a, water-soluble; oil-insoluble petroof breaking etx-oleum emu!- moorporefing therein e composition having so a component the N-omlkyleteol sulfonamide of a water-soluble, oil-insoluble petroleum sulfonioeoid,

5. A petroleum d 2 mg comooemon which comprises as e componene the N-olleteel e3:

suifonemlde of. e wefier eoluble, oil-ohms petroleum sulfohio aoi fi.

ii. A petroleum dem composition which comprises as e, component the Marlowe monosulfonemide of e weteoeoluble, Oil-r 1-: 1w petroleum sufifomo erode:

7. A petroleum dem= disulfode of e weter-soluble, oil-ole petroleum sulfonic acid,

8. Apetroleum 1 m; comp comma which comprises m e eomponeoo the 'monoeulfonemlde oi o water-soluble, wi -om .ble petroleum onfie we composition which I comprises as a component than. a. fonemide of e water soluble, oil-insoluble petio- J 1mg composition which oomprisee as e. eomoonmt h 

